JP5506325B2 - toner - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic latent image used for developing an electrostatic latent image in electrophotography and electrostatic recording. More specifically, the present invention relates to a toner used in an image recording apparatus that can be used for a copying machine, a printer, a facsimile, and the like.

  In recent years, the technological trend of printers has progressed toward the miniaturization and speeding up of machines, and the environment in which printers are used has become various usages and environments regardless of whether they are home or office. With the diversification of printer usage environments described above, printers are used in a wide range of environments, from those where it is difficult to obtain electrification represented by high-temperature and high-humidity environments, to environments where overcharging such as low-temperature and low-humidity environments are likely to occur. It is coming.

  In general, under a high temperature and high humidity environment, there is a problem such as so-called fogging in which poorly charged toner is printed even on a white background portion of an image due to toner charging failure, or a so-called transfer failure in which the poorly charged toner is not sufficiently transferred. It has been reported. In particular, when thick paper is used, heat is easily taken away from the paper surface, so it is necessary to increase the amount of heat applied to the toner in order to sufficiently fix the toner. As a result, the fogging problem tends to appear more noticeably when compared with normal paper. Further, when left in a high-temperature and high-humidity environment, the toner is less likely to be charged due to the moisture absorption of the toner and the charging member, and there is a tendency that an adverse effect due to charging failure is more likely to occur than usual.

  On the other hand, due to diversification of printer usage environments, the temperature has become low near 0 ° C. at night, and printers have been used even in cold regions where the temperature is very low and low in the daytime. In the above-mentioned extremely low temperature and low humidity environment, the toner is likely to be overcharged, and problems such as poor transfer due to an increase in electrostatic adhesion of the toner and poor regulation of the toner due to an increase in the degree of electrostatic cohesion have been used. It tends to occur more easily than in the environment. For these reasons, there is a demand for a toner capable of maintaining stable charging performance under any environment.

  As one technique for improving the charging performance, it has been reported that the charging stability can be improved by melting and kneading a salt-like structured silicate in a toner as a charge control agent (for example, Patent Documents 1 and 2). reference). In addition, by mixing zeolite in a charge control resin having a sulfonic acid group as a substituent, capping the sulfonic acid group with the pores of the zeolite can suppress a decrease in chargeability in a high temperature and high humidity environment. Has been reported (for example, see Patent Document 3). However, since the zeolite used in the above study has a high aluminum ratio in the zeolite and the water absorption of the zeolite itself is high, it is difficult to say that the charge control in a high temperature and high humidity environment is sufficient. Furthermore, in the above study, zeolite is present in the toner, and the effect of improving frictional charging by adding zeolite is small. Especially, sufficient charge rising performance is obtained in printing after leaving for a while after mass printing in a high temperature and high humidity environment. It was found that there were problems that could not be obtained.

  In addition, it has been reported that the charging performance after mass printing is improved by attaching zeolite particles to toner particles and suppressing member contamination (see, for example, Patent Document 4). However, the zeolite in the above study has a problem of the rising property of charging in a high temperature and high humidity environment because the ratio of aluminum in the zeolite is large and the water absorption of the zeolite itself is high.

  As described above, with conventional toners, satisfactory images cannot be obtained satisfactorily in any use environment on high-speed and long-life machines currently required in the market, and further improvements are desired. is there.

JP-T-2003-515795 JP 2007-241187 A Japanese Patent Laying-Open No. 2005-070520 JP 2002-244339 A

An object of the present invention is to provide a toner that solves the above problems.
That is, by having good charging performance in any environment, even when left in a high-temperature and high-humidity environment, fog hardly occurs during development, and also during development in an extremely low-temperature and low-humidity environment, An object of the present invention is to provide a toner that does not easily cause transfer defects.

As a result of intensive studies, the present inventors have found that the above problem can be solved by the following configuration, and have completed the present invention.
That is, according to the present invention, in a toner in which zeolite is externally added to toner particles, the zeolite contains at least silicon atoms and aluminum atoms, and the ratio of aluminum atoms to the total of silicon atoms and aluminum atoms contained in the zeolite (% ) Is 0.3 to 22.5 .

According to the present invention, good charging performance is exhibited even in a high temperature and high humidity environment, and overcharging can be suppressed in a very low temperature and low humidity environment.
That is, it is possible to provide a toner that hardly causes fogging when left in a high-temperature and high-humidity environment and does not easily cause transfer failure in an extremely low-temperature and low-humidity environment.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention.
The toner of the present invention is a toner obtained by externally adding zeolite to toner particles, wherein the zeolite contains at least silicon atoms and aluminum atoms, and the ratio of aluminum atoms to the total of silicon atoms and aluminum atoms contained in the zeolite (% ) Satisfies the relationship of 0.2 to 24.0.

In general, zeolite is a general term for aluminosilicate having fine pores in a crystal, and has regular fine pores in the crystal.
The basic unit of the structure of the aluminosilicate is a tetrahedral (SiO ₄ ) 4- and (AlO ₄ ) 5-unit (together referred to as TO4 units), and one TO4 unit has four apex oxygens. By sharing with each of the adjacent four TO4 units, they are three-dimensionally connected one after another to form crystals ("Zeolite Science and Engineering" Kodansha Scientific).

Note that metallosilicates in which aluminum of crystalline porous aluminosilicate is replaced with other metals are also included in the zeolite, but the zeolite used in the present invention has at least silicon element and aluminum as elements constituting the zeolite. It is a zeolite containing elements.

  In general, it is reported that silicon atoms are bonded to aluminum atoms and oxygen atoms in zeolites, and it is considered that silicon atoms and aluminum atoms are present in zeolites in a highly dispersed state. ("Amer. Mineral." 39, 92 (1954)).

In addition, zeolite has a structure in which cations such as Na ⁺ and H ⁺ are distributed in the structure because the skeleton itself has a negative charge due to the presence of aluminum atoms in the silicon skeleton.

Generally, the charging series of toner particles and silica is almost the same, but it is known that alumina has a positive chargeability than toner particles.
Therefore, it is considered that in the zeolite, which is a kind of composite oxide of silica and alumina, the chargeability of the toner is improved by the frictional charging between the aluminum atom portion having positive chargeability and the toner particles.

  However, generally used zeolites have a high aluminum content in the crystal structure, more hydrophilic alumina parts, and higher water absorption of the zeolite, increasing moisture adsorption in high-temperature and high-humidity environments. Tended to be.

As a result of intensive studies, the inventors of the present invention externally added a zeolite (high silica zeolite) in which the amount of aluminum atoms in the crystal is controlled to an appropriate amount to the toner particles, thereby preventing poor charging in a high temperature and high humidity environment. It was found that excessive charging in an extremely low temperature and low humidity environment can be suppressed.
That is, it has been found that even when the toner is left in a high-temperature and high-humidity environment, the problem of so-called fogging in which the poorly charged toner is printed on the white background portion of the image is found to be small.
On the other hand, it has been found that, under an extremely low temperature and low humidity environment, it is possible to suppress overcharging of toner particles, and transfer defects due to an increase in electrostatic adhesion force of toner due to overcharging are reduced.
Although the specific mechanism is not clear, the present inventors presume as follows.

Unlike simple silica-alumina composite oxides, zeolite has a regular crystal structure in which aluminum atoms are highly dispersed in the crystal structure, so it is considered that aluminum atoms on the crystal surface are also highly dispersed. .
Furthermore, since zeolite is a porous material having regular pores, it is difficult for a portion where aluminum atoms on the crystal surface are locally concentrated to exist, and this is a local problem when compared with a simple silica-alumina composite oxide. Water adsorption is unlikely to occur.

  Since the aluminum element content in the zeolite of the present invention is smaller than that of a general zeolite, it is considered that it is less susceptible to moisture adsorption even when compared with a general zeolite.

  In the toner of the present invention, since zeolite is externally added to the toner particles, it is considered that the effect of improving the triboelectric charging performance of the toner itself can be obtained more easily by friction between the aluminum atoms in the zeolite and the toner particles. ing.

Furthermore, since aluminum atoms are highly dispersed in the crystal structure and the zeolite itself is a porous body, a sufficient charge rising effect can be achieved even with a small amount of aluminum compared to a simple silica-alumina composite oxide. I think I have it.
Therefore, even when the toner of the present invention is left in a high-temperature and high-humidity environment, the zeolite does not excessively adsorb moisture, and highly dispersed aluminum atoms significantly improve the charge rising performance due to frictional charging between the toners. thinking.
On the other hand, in a low-temperature and low-humidity environment, it is possible to retain moderate moisture that is not excessive in the crystal because it is a porous material with many hydrophobic silica components, and the moisture suppresses overcharge. I believe.

The ratio (%) of aluminum atoms to the total of silicon atoms and aluminum atoms contained in the zeolite used in the toner of the present invention is 0.2 to 24.0. From the viewpoint of further improving the effect of the present invention, 0 It is preferably 2 to 12.0, and more preferably 1.5 to 12.0.
When the proportion of aluminum atoms is less than 0.2%, the effect of the aluminum element is reduced, the effect of starting up the charge in a high-temperature and high-humidity environment is insufficient, and overcharge is likely to occur in a low-temperature and low-humidity environment It is because it is in a tendency.
Further, when the proportion of aluminum atoms is larger than 24.0%, the effect of water absorption of aluminum atoms is large, and there is a tendency that poor charging is likely to occur in a high temperature and high humidity environment.
Zeolite and silica-alumina composite oxide can be distinguished from each other depending on whether or not they have a crystal structure by measuring X-ray diffraction using an X-ray diffractometer.

The zeolite has a BET specific surface area of preferably 350 m ² / g or more and 750 m ² / g or less, more preferably 500 m ² / g or more and 700 m ² / g or less.
When the BET specific surface area is smaller than 350 m ² / g, the dispersibility of aluminum atoms in the crystal becomes small, and the effect of improving the charging performance by the aluminum atoms tends to be difficult to obtain. In addition, since it is difficult to physically adsorb moisture in the crystal, the effect of suppressing charge-up in a low temperature and low humidity environment tends to be small.

The primary particle diameter D50y (μm) of the zeolite is preferably 0.01 ≦ D50y ≦ 1.50, and more preferably 0.05 ≦ D50y ≦ 0.50.
If D50y is smaller than 0.01, it is difficult to obtain the effect of the invention due to the pores of the zeolite,
Furthermore, the stability as a zeolite tends to be impaired.
On the other hand, if D50y is larger than 1.50, it tends to be difficult to uniformly add the toner particles to the toner particles.

The secondary particle diameter D50z (μm) of the zeolite is preferably 0.10 ≦ D50z ≦ 7.00, and more preferably 0.20 ≦ D50z ≦ 3.50.
When D50z is smaller than 0.10, the particle size of the zeolite primary particles forming it tends to be small, and the effect that the zeolite has pores tends to be difficult to obtain.
Further, when D50z is larger than 7.00, the secondary particle diameter of the zeolite is about the same as or larger than that of the toner, so that when zeolite is externally added, the zeolite is uniformly formed on the toner surface. It tends to be difficult to exist.

Although the crystal structure of the zeolite in this invention is not limited at all, the following structures are illustrated. Sodalite (SOD), AlPO4-11 (AEL), EU-1 (EUO), Ferrierite (FER), Hulandite (HEU), ZSM-5 (MFI), NU-87 (NES), Theta-1 ( TON), Weinebeite (WEI), AlPO4-5 (AFI), AlPO4-31 (ATO), Beta (BEA), CIT-1 (CON), X (FAU), Y (FAU), USY (FAU), Hoja Site (FAU), L (LTL), Mordenite (MOR), Cancrinite (CAN) Gmelinite (GME), ZSM-12 (MTW), Offretite (OFF), Cloverite (-CLO), VPI-5 (VFI) AlPO4-8 (AET), CIT-5 (CFI), UTD-1
(DON).
Here, the symbol in parentheses attached to the zeolite name exemplified above means a structure code (source: WH Meier, DH Olson, Ch. Baelocher ed., Atlas of Zeolite Structure Types, 4th. Ed., Elsevier, 1996).

Moreover, the following are illustrated as a cation seed | species in a zeolite.
H ⁺ , NH ^{4 +} , Ag ⁺ , K ⁺ , Li ⁺ , Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Sr ²⁺ , Zn ²⁺ , Pb ²⁺ , Ni ²⁺ , Cu ²⁺ , Co ²⁺ , Mn ²⁺ , or combinations thereof.
These zeolites can be used alone or in combination of two or more.

The crystal shape of the zeolite of the present invention is not particularly limited.
For example, a polyhedral shape, a spherical shape, a needle shape and the like can be exemplified. Among these shapes, a shape closer to a spherical shape is preferable in that good triboelectric charging occurs when externally added to toner particles.

The amount of the zeolite added is preferably 0.01 to 5.00 parts by mass, more preferably 0.10 parts by mass to 2.00 parts by mass with respect to 100.00 parts by mass of the toner particles.
When the amount is less than 0.01 parts by mass, the effect of improving the charging performance due to the addition of the zeolite tends to be difficult to obtain. When the amount is more than 5.00 parts by mass, member contamination or the like tends to occur.

  As the zeolite used in the present invention, a commercially available product in which the ratio of silicon atom and aluminum atom is within the range defined in the present invention can be used.

The toner particles of the present invention preferably contain a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group.
Specifically, polymers and copolymers having a sulfonic acid group or a sulfonate group having the following structure are exemplified.
X (SO ₃ ⁻ ) n · mY ^{k +}
(X represents a polymer site or copolymer site derived from a polymerizable monomer, Y ^{k +} represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m.)

In this case, the counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, and ammonium ions.
Examples of the polymer or copolymer include a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group, such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-methacrylic acid. Examples thereof include a polymer or copolymer containing one or more monomers selected from the group consisting of amido-2-methylpropanesulfonic acid, vinylsulfonic acid, methacrylsulfonic acid, and alkyl esters thereof as a constituent component. .

  In addition to the above monomers, examples of monomers that form a copolymer with the above monomers include vinyl polymer monomers, which are monofunctional polymerizable monomers or polyfunctional polymerizable monomers. A mer can be used.

In the case of a copolymer, the form is not particularly limited, and examples thereof include a random copolymer, a block copolymer, and a graft copolymer. The molecular weight of the polymer or copolymer is not particularly limited, but preferably Mn is 5000 to 30000, and Mw is 10,000 to 5000.
0.

  In the case of a copolymer, the ratio of the monomer having a sulfonic acid group or the like to the whole monomer constituting the copolymer is 2.0 to 14.0% by mass.

  By containing the polymer or copolymer, the charging stability in a high-temperature and high-humidity environment is further enhanced, and the polymer or copolymer has a high negative chargeability, so There is a tendency that the charge rising property of the toner particles is further improved by frictional charging.

The amount of the polymer or copolymer added is preferably 0.01 to 20.00 parts by mass, more preferably 100.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer constituting the binder resin in the toner particles. Is 0.30 parts by mass to 10.00 parts by mass.
If the amount is less than 0.01 parts by mass, the effect of charging stability by the polymer or copolymer tends to be difficult to obtain.
Further, when the amount is more than 20.00 parts by mass, the toner particles easily adsorb moisture in the air, the charging stability in a high humidity environment is likely to decrease, and the charging is likely to be excessive in a low humidity environment. There is a tendency.

The method for producing the toner particles constituting the toner of the present invention is not particularly limited, and a known production method can be used.
Among the known production methods, the toner particles of the present invention are prepared by adding a polymerizable monomer composition containing at least a polymerizable monomer and a colorant to an aqueous medium, and then adding the polymerizable monomer composition in the aqueous medium. It is preferably obtained by granulating to form a polymerizable monomer composition particle and polymerizing the polymerizable monomer contained in the polymerizable monomer composition particle.
The toner particles synthesized by such a granulation method have a sharp particle size distribution, and it is easy to obtain a toner with a high degree of circularity, which tends to obtain excellent charging performance by increasing the fluidity of the toner and causing tribocharging. It is in.

  In particular, when the polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group described above is contained, the polymer is likely to be present on the toner particle surface, and the polymer is added. It tends to be effective.

Hereinafter, the most suitable suspension polymerization method for obtaining the toner particles used in the present invention will be exemplified to describe the toner particle production method.
Other additives such as a polymerizable monomer, a colorant, a polar resin as necessary, and a release agent are uniformly dissolved or dispersed by a disperser such as a homogenizer, ball mill, colloid mill, or ultrasonic disperser. In this, a polymerization initiator is dissolved to prepare a polymerizable monomer composition.
Next, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer and then granulated to form particles, and toner particles are produced by polymerizing the polymerizable monomer in the particles. .
The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before the polymerizable monomer composition is dispersed in the aqueous medium.
Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

  In the present invention, it is preferable to add an appropriate acid for pH adjustment at the time of dispersion, granulation, and before starting the polymerization reaction. As the acid used in the toner of the present invention, generally used acids such as hydrochloric acid, sulfuric acid and nitric acid can be used. By adjusting the aqueous solution during polymerization to an appropriate pH, it is possible to obtain a toner having more uniform charging performance.

When the toner particles of the present invention contain a polar resin, the addition of the polar resin during the polymerization reaction from the dispersion step of the polymerizable monomer composition to the polymerization step causes the polymerizable monomer composition and the aqueous dispersion to become toner particles. The presence state of the polar resin can be controlled according to the balance of polarity exhibited by the medium.
That is, by adding a polar resin, functional separation according to the resin layer is possible. Further, the toner particles obtained by the suspension polymerization method are preferable because they have a core-shell structure including a release agent component.

Examples of the polar resin include polyester resin, epoxy resin, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and styrene-maleic acid copolymer.
A polyester resin is particularly preferable, and the acid value is preferably in the range of 4 to 20 mgKOH / g. When the acid value is less than 4 mgKOH / g, it is difficult to form a shell structure and the rise of charging is slow, and it tends to cause problems such as a decrease in image density and fogging.
When the acid value exceeds 20 mgKOH / g, the chargeability is affected and the developability tends to deteriorate. The molecular weight of 3,000 to 30,000 is preferably a main peak molecular weight because the fluidity and negative frictional charging characteristics of the toner particles can be improved.
A preferable addition amount of the polar resin is 1 to 25 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer constituting the binder resin.
If the amount is less than 1 part by mass, the presence state of the polar resin in the toner particles tends to be uneven, whereas if it exceeds 25 parts by mass, the layer of the polar resin formed on the surface of the toner particles tends to be thick. Therefore, it is not preferable.

As the polymerizable monomer constituting the binder resin used in the toner of the present invention, generally used styrene-acrylic copolymer, styrene-methacrylic copolymer, epoxy resin, styrene-butadiene copolymer are used. Can be mentioned.
As the polymerizable monomer constituting the binder resin, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Examples of the polymerizable monomer for constituting the binder resin include the following. Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.

These polymerizable monomers are used alone or in general, and have a theoretical glass transition point (Tg) described in publication polymer handbook 2nd edition III-p139 to 192 (John Wiley & Sons) of 40 ° C. to A plurality of polymerizable monomers are appropriately mixed and used so as to exhibit 75 ° C.
When the theoretical glass transition point of the polymerizable monomer mixture is less than 40 ° C., problems are likely to occur from the viewpoint of the durability stability of the toner, and when it exceeds 75 ° C., the glossiness at the time of low-temperature fixing is lowered. .

In the present invention, it is possible to add a low molecular weight polymer in order to make the THF (tetrahydrofuran) soluble component of the toner have a preferable molecular weight distribution and improve the low-temperature fixing performance.
The low molecular weight polymer can be added to the polymerizable monomer composition when toner particles are produced by suspension polymerization.
As the low molecular weight polymer, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 2,000 to 5,000, and Mw / Mn is less than 4.5, preferably 3 Those less than 0.0 are preferred in terms of fixability and developability.
Examples of low molecular weight polymers include:
Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin.
In addition, the said low molecular weight polymer can be used individually or in mixture.

  Among these low molecular weight polymers, the glass transition point of the low molecular weight polymer is preferably 40 to 100 ° C. If the glass transition point is less than 40 ° C., the toner particles tend to deteriorate. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur. The glass transition point of the low molecular weight resin is preferably 40 to 70 ° C., more preferably 40 to 65 ° C. from the viewpoint that low temperature fixability can be obtained.

The amount of the low molecular weight polymer added is preferably 0.1 to 75.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer constituting the binder resin in the toner particles. If the amount is less than 0.1 parts by mass in 100.0 parts by mass of the polymerizable monomer constituting the binder resin in the toner particles, the effect of adding the low molecular weight resin is small.
On the other hand, when it is 75.0 parts by mass or more, the durability of the toner particles tends to be lowered.

In the present invention, a crosslinking agent may be used when the binder resin is synthesized in order to increase the mechanical strength of the toner particles and to control the molecular weight of the THF soluble component of the toner.
Examples of the bifunctional crosslinking agent include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and dimethacrylate instead of diacrylate Thing.
The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate.
The addition amount of these crosslinking agents is preferably 0.05 to 10.00 parts by mass, more preferably 0.10 to 5.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. Part.

The release agent that can be used in the present invention is preferably a hydrocarbon-based release agent, and the content of the release agent component is preferably 4.10 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. 0 parts by mass to 2
The amount is 5.0 parts by mass, more preferably 7.0 parts by mass to 15.0 parts by mass.
If the release agent content is less than 4.0 parts by mass, sufficient glossiness cannot be obtained at low temperature fixing. On the other hand, if it is larger than 25.0 parts by mass, the durability is lowered.
Furthermore, the release agent preferably has a maximum endothermic peak temperature in the range of 40 ° C. to 110 ° C., more preferably, in the DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) device. 45 ° C to 90 ° C.
When the maximum endothermic peak temperature is less than 40 ° C., the durability of the toner decreases. On the other hand, when the maximum endothermic peak temperature exceeds 110 ° C., the glossiness at the time of low-temperature fixing decreases.
The release agent used in the present invention is particularly preferably a release agent having a small polar component such as a hydrocarbon-based release agent in that it is easily encapsulated in the toner particle central part.
Examples of other mold release agents include the following. Amide waxes, higher fatty acids, long chain alcohols, ketone waxes, ester waxes, and derivatives such as these graft compounds and block compounds. If necessary, two or more release agents may be used in combination.
Examples of the hydrocarbon release agent include the following. Petroleum wax such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof; Fischer-Tropsch wax and derivatives thereof according to Fischer-Tropsch method; polyolefin wax such as polyethylene wax and polypropylene wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.
Further examples include hydrogenated castor oil and derivatives thereof, vegetable waxes and animal waxes. These waxes can be used alone or in combination of two or more.
Note that an antioxidant may be added to these hydrocarbon release agents as long as the chargeability of the toner is not affected.

Examples of the polymerization initiator that can be used in the toner of the present invention include the following.
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.
The amount of these polymerization initiators used varies depending on the desired degree of polymerization, but is generally 3 to 20 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer.
The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.
Specific examples include the following.
C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue.

Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds.
Specific examples include the following.
C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

Examples of the organic pigment or organic dye as the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Specific examples include the following.
C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

Examples of the black colorant include carbon black and those prepared by using the yellow colorant / magenta colorant / cyan colorant toned to black.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.
The colorant is preferably used by adding 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  In the present invention, when toner particles are obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably, a hydrophobic treatment with a substance that does not inhibit polymerization is performed. It is better to apply it to the colorant. In particular, since dye-based colorants and carbon black have many polymerization-inhibiting properties, care must be taken when using them. In addition, as a method for suppressing the polymerization inhibitory property of the dye-based colorant, a method of polymerizing a polymerizable monomer in the presence of these dyes in advance can be mentioned, and the obtained colored polymer is composed of a polymerizable monomer composition. Add to product. Moreover, about carbon black, you may process with the substance (for example, polyorganosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

As the dispersion stabilizer used when preparing the aqueous medium, known inorganic and organic dispersion stabilizers can be used.
Specifically, the following are mentioned as an example of an inorganic dispersion stabilizer.
Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina .
Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

As the dispersion stabilizer used in preparing the aqueous medium used in the toner of the present invention, an inorganic poorly water-soluble dispersion stabilizer is preferable, and it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid. .
In the present invention, when an aqueous medium is prepared, the amount of these dispersion stabilizers used is 0.2 to 2.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. Preferably there is.

In the present invention, it is preferable to prepare an aqueous medium using 300 parts by mass to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.
In the present invention, when preparing an aqueous medium in which the above dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is.
In order to obtain particles of a dispersion stabilizer having a fine uniform particle size, an aqueous medium may be prepared by generating a dispersion stabilizer in a liquid medium such as water under high-speed stirring.
For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By adding a charge control agent, it is possible to improve and stabilize the charge characteristics, and to control the optimum triboelectric charge amount according to the development system.
As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.
Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and a small amount of solubilized products in an aqueous medium is particularly preferable.
Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds.

  Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Among these, the polymer having a sulfonic acid functional group described above as a charge control agent is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group, for the reason described above. preferable.

The toner of the present invention can contain these charge control agents alone or in combination of two or more.
A preferable blending amount of the charge control agent is 0.01 to 20.00 parts by mass, more preferably 0.30 to 10.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. .

In the toner of the present invention, inorganic fine powder can be externally added as necessary.
Examples of the inorganic fine powder include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, and double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.
Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass.
As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable.
The dry silica may be a composite fine powder of silica and another metal oxide by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

The inorganic fine powder is externally added to the toner particles in order to improve the fluidity of the toner and to make the toner particles uniform.
Hydrophobic treatment of the inorganic fine powder makes it possible to adjust the charge amount of the toner, improve environmental stability, and improve characteristics in a high-humidity environment. Is preferably used.
When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner decreases, and the developability and transferability tend to decrease, and the durability in a harsh environment tends to decrease.

Non-modified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds are used as hydrophobic treatment agents for inorganic fine powders. Can be mentioned. These treatment agents may be used alone or in combination.
Among these, inorganic fine powder treated with silicone oil is preferable.
More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or after the hydrophobization treatment, the hydrophobized inorganic fine powder treated with silicone oil maintains a high charge amount of toner particles even in a high humidity environment, and is stable. The point which can provide the done image is good.
The total amount of the inorganic fine powder is preferably 1.0 to 5.0 parts by mass with respect to 100.0 parts by mass of the toner particles.

  The apparatus used in the external addition process of the present invention is not particularly limited as long as the characteristics can be achieved, and a known manufacturing method can be used. However, as an example of the apparatus, existing apparatuses such as a Henschel mixer and a super mixer can be used. A high-speed stirring type mixer can be mentioned.

Next, various measurement methods in the present invention will be described.
<Measurement of ratio (%) of aluminum atom to total of silicon atom and aluminum atom contained in zeolite>
The measurement of the ratio of aluminum atoms to the total of silicon atoms and aluminum atoms in the zeolite used in the present invention can be obtained with a fluorescent X-ray analyzer. The measurement method in the present invention will be described below.
Using a wavelength dispersive X-ray fluorescence analyzer Axios advanced (manufactured by PANalytical), the elements from Na to U in the zeolite are directly measured by the FP method in a He atmosphere.
At that time, it is assumed that all the detected elements are oxides, and their total mass is assumed to be 100%. Software UniQuant (registered trademark) 5 (ver. 5.49) (distributor: manufactured by PANalytical) is used. Then, the content (mass%) of SiO ₂ and / or Al ₂ O ₃ with respect to the total mass is determined as an oxide equivalent value.
Next, the abundance ratio of silicon atoms and aluminum atoms is calculated from the obtained content, and the ratio (%) of aluminum atoms to the total of silicon atoms and aluminum atoms is calculated from the following formula (1).

<Measurement of BET specific surface area of zeolite>
The BET specific surface area of the zeolite is measured according to JIS Z8830 (2001). A specific measurement method is as follows.
As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

The BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed to zeolite, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the toner at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the zeolite, is determined by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.
Furthermore, the BET specific surface area S (m ² · g ⁻¹ ) of the zeolite is calculated from the calculated Vm and the molecular occupation cross-sectional area of the nitrogen molecule (0.162 nm ² ) based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)

The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.15 g of zeolite is put into the sample cell using a funnel.
The sample cell containing the zeolite is set in a “pretreatment apparatus Bacuprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. During vacuum deaeration, the toner is gradually deaerated while adjusting the valve so that the toner is not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate toner mass is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the zeolite in the sample cell is not contaminated by moisture in the atmosphere.
Next, a special “isothermal jacket” is attached to the stem portion of the sample cell containing zeolite. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.

Subsequently, the free space of the sample cell including the connection tool is measured. Free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen in the same manner using helium gas. Calculated from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.
Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules on the zeolite. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Furthermore, using the value of Vm, the BET specific surface area of the zeolite is calculated as described above.

<Measurement of primary particle diameter D50y of zeolite particles>
The measurement of the primary particle diameter D50y of the zeolite particles used in the present invention can be obtained using FE-SEM (S-800) manufactured by Hitachi.
First, a digital observation image enlarged at a magnification of 10,000 times was obtained. Next, the primary particle diameter D50y of the zeolite is measured from the digital image using image processing software Win-Roof (distributor: Mitani Corporation) as follows.
It was obtained by paying attention to one primary particle of zeolite crystal on the image, calculating the equivalent circle diameter of the primary particle from the area of one primary particle, and measuring the equivalent circle diameter of 100 randomly selected particles. The volume-based median diameter D50y is calculated from the particle diameter.

<Measurement of secondary particle size D50z of zeolite particles>
The volume-based median diameter (D50z) of the zeolite particles used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used.
Setting of measurement conditions and analysis of measurement data are performed with the dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) included with LA-920.
Ver. 2.02 "is used.
As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.
The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “118A000I” (relative refractive index 1.18).
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, optical axis adjustment, optical axis fine adjustment, and blank measurement are performed.
(7) Put about 60 ml of ion-exchanged water in a glass 100 ml flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass is added.
(8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of zeolite is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds.
In this case, the zeolite may become solid and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the mass is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(11) The aqueous solution in which the zeolite prepared in the above (10) is dispersed is immediately added little by little to the batch type cell while taking care not to enter bubbles, and the transmittance of the tungsten lamp becomes 90% to 95%. Adjust as follows.
Then, the particle size distribution is measured. Based on the obtained volume-based particle size distribution data, the volume-based median diameter (D50z) is calculated.

<Measurement of volume-based median diameter D50t of toner particles>
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used.
For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, dedicated software was set up as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using
By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm.
Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker.
In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared.
A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds.
In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the number-based median diameter D50t is calculated. The “average diameter” on the “analysis / number statistical value (arithmetic average)” screen when the graph / number% is set in the dedicated software is the median diameter D50t based on the number of toners.

また、円形度標準偏差ＳＤは、平均円形度Ｃ、各粒子における円形度ｃｉ、測定粒子数をｍとすると下記式（３）から算出される。

<Measurement of average circularity of toner>
The average circularity of the toner is measured using a flow type particle image measuring device “FPIA-2100” (manufactured by Sysmex Corporation). Details are as follows.
First, the circularity is calculated from the following equation.
Circularity = (perimeter of a circle having the same area as the particle projection area) / (perimeter of the particle projection image)
Here, the “particle projected area” is the area of the binarized particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the particle image. .
The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).
In the present invention, the circularity is an index indicating the degree of unevenness of the particles, and is 1.000 when the particles are perfectly spherical. The more complicated the surface shape, the smaller the circularity.
The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following formula (2), where ci is the circularity at the dividing point i of the particle size distribution and m is the number of measured particles.

The circularity standard deviation SD is calculated from the following equation (3) where the average circularity C, the circularity ci of each particle, and the number of measured particles are m.

A specific measurement method is as follows.
First, about 10 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container.
In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.1 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass.
Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement.
As an ultrasonic disperser, two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser with an electric output of 120 W “Ultrasonic Dispense System Tetora 150 type” (manufactured by Nikkei Bios) Is used.
A predetermined amount of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.
Further, in order to suppress variation in circularity, the installation environment of the apparatus is controlled to 23 ° C. ± 0.5 ° C. so that the in-machine temperature of the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C.
In addition, automatic focus adjustment is performed using standard latex particles of 2 μm at regular intervals, preferably every 2 hours (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) is diluted with ion-exchanged water. Do.
The flow type particle image measuring apparatus was used for measuring the circularity of the toner particles, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid.
The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and the concentration of the dispersion is readjusted and measured so that the toner particle concentration at the time of measurement is about 5000 particles / μl. After the measurement, the average circularity of the toner in the range of the circle equivalent diameter of 2.00 μm or more and less than 40.02 μm is obtained using this data.
The equivalent circle diameter is a value calculated as follows.
Equivalent circle diameter = (particle projected area / π) ^1/2 × 2
“FPIA-2100”, which is a measuring apparatus used in the present invention, has a thinner sheath flow (7 μm → 4 μm) than “FPIA-1000” which has been used for observing the shape of a conventional toner. ) And the magnification of the processed particle image.
In addition, the processing resolution of the captured image is improved (256 × 256 → 512 × 512), and the accuracy of toner shape measurement is improved.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, the number of parts in the following composition is part by mass unless otherwise specified.
[Production example of negative charge control agent (1)]
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As monomers, 88 parts by mass of styrene, 6.5 parts by mass of 2-ethylhexyl acrylate, and 4.8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature while stirring.
A solution obtained by diluting 1 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours.
Further, a solution obtained by diluting 1 part by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and further stirred for 5 hours to complete the polymerization.
Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill.
The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, MEK (methyl ethyl ketone) was added to dissolve the particles to a concentration of 10%, and the above solution was gradually poured into 20 times the amount of MEK in methanol for reprecipitation.
The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.
Further, MEK was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the above solution was gradually poured into n-hexane 20 times the amount of MEK for reprecipitation.
The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.
The polar polymer thus obtained had a Tg of about 83 ° C. and a main peak molecular weight (Mp) of 215000, Mn 11900, and Mw 31500.
Further, the composition measured by 1H-NMR (EX-400: 400 MHz manufactured by JEOL Ltd.) was as charged. Let the obtained resin be a negative charge control agent (1).

[Production Example of Toner Particle (1)]
In a four-necked vessel, 60.0 parts by mass of ion-exchanged water, 300.00 parts by mass of a 0.1 mol / liter sodium phosphate aqueous solution and 10.00 parts by mass of 1.00 mol / liter-hydrochloric acid were added, The mixture was stirred at 12,000 rpm using a stirrer TK-homomixer and kept at 60 ° C.
Here, 25.00 parts by mass of a 1.00 mol / liter-CaCl ₂ aqueous solution was added at a time to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

-Styrene monomer 78.00 mass parts-n-butyl acrylate 22.00 mass parts-C.I. I. Pigment Blue 15: 3 8.00 parts by mass / styrene resin (polystyrene Mw = 2880, Mw / Mn = 2.2) 20.00
Mass parts / Polyester resin (isophthalic acid-propylene oxide modified bisphenol A (2 mol adduct) -propylene oxide modified bisphenol A (3 mol adduct) (molar ratio 30:55:15)) 8.00 mass parts / load Electricity control agent (1) 0.30 parts by mass, negative charge control agent (Orient Chemical Industries, Ltd .: Bontron E88)) 0.70 parts by mass, wax (Nippon Seiwa: HNP-10) 12.50 parts by mass Part Using the TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the above materials are dispersed under the condition of 5,000 rpm, and then heated to 65 ° C. to uniformly dissolve and disperse the polymerizable monomer composition. A product was prepared.
After adding 7.5 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (75% toluene solution) as a polymerization initiator to the polymerizable monomer composition, a stirrer Was put into an aqueous dispersion medium having a rotational speed of 12,000 rpm.
And it granulated for 10 minutes, maintaining a rotation speed at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 67 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring.
Next, the temperature in the container was raised to 80 ° C. and maintained for 40 minutes, and the vessel was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute, whereby slurry 1 was obtained. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer.
Further, after filtering, washing, and drying, classification was performed using a multi-division classifier using the Coanda effect to obtain toner particles (1) having a number-based median diameter D50t of 6.3 μm. The average circularity of the obtained toner particles (1) was 0.985.

[Production Example of Toner Particles (2)]
Toner particles (2) were obtained in the same manner as toner particles (1) except that the amount of negative charge control agent (1) added to toner particles (1) was changed from 0.30 parts to 0.70 parts. The number-based median diameter D50t of the obtained toner particles (2) is 6.5 μm, and the average circularity is 0.98.
0.

[Production Example of Toner Particle (3)]
Toner particles (3) were obtained in the same manner as toner particles (1) except that the negative charge control agent (1) was not added to the toner particles (1). The number-based median diameter D50t of the obtained toner particles (3) was 7.2 μm, and the average circularity was 0.975.

上記材料をヘンシェルミキサーにより十分予備混合し、二軸押出し混練機で任意のバレル温度にて溶融混練した。前記融解混練した材料を、冷却後ハンマーミルを用いて粗粉砕し、第一段階として機械式粉砕方式による微粉砕機で１０μｍ以下の粒径に微粉砕した。
さらに、第二段階として、上記第一段階の工程により得られた微粉砕物を、粉砕条件を変更した機械式粉砕機により更に粉砕処理し、第二段階の工程により得られた微粉砕物を熱球形化装置によって６７℃で処理した。
その後、上記工程により得られた微粉砕物を分級及び機械式衝撃力を用いる表面改質処理を同時に行う装置にて分級および球形化し、個数基準のメジアン径Ｄ５０ｔが８．１μｍのトナー粒子（４）を得た。
トナー粒子（４）の平均円形度は０．９７０であった。 [Production Example of Toner Particles (4)]
Binder resin [polyester resin (1) *] 100.00 parts by mass I. Pigment Blue 15: 3 5.00 parts by mass, negative charge control agent (1) 0.30 parts by weight, negative charge control agent (Orient Chemical Industries, Ltd .: Bontron E88)) 0.60 parts by weight, wax (Nippon Seiwa) Manufactured by: HNP-10) 5.00 parts by mass / divinylbenzene 0.30 parts by mass * The monomer composition ratio used in the polyester resin (1) is shown below.
Fumaric acid 21 mol%
Terephthalic acid 11mol%
Trimellitic acid 9mol%
as well as,
Diol component represented by (x + y = 3.0) in the structure represented by the following formula [Chemical Formula 1]
59 mol%

The above materials were sufficiently premixed with a Henschel mixer, and melt kneaded at an arbitrary barrel temperature with a twin screw extrusion kneader. The melt-kneaded material was cooled and coarsely pulverized using a hammer mill, and as a first step, it was finely pulverized to a particle size of 10 μm or less with a mechanical pulverizer.
Further, as the second stage, the finely pulverized product obtained by the first stage process is further pulverized by a mechanical pulverizer whose pulverization conditions are changed, and the finely pulverized substance obtained by the second stage process is obtained. Processed at 67 ° C. with a hot spheronizer.
Thereafter, the finely pulverized product obtained in the above step is classified and spheroidized by an apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force, and toner particles (4 having a number-based median diameter D50t of 8.1 μm). )
The average circularity of the toner particles (4) was 0.970.

[Production Example of Toner Particle (5)]
Toner particles (5) were obtained in the same manner as toner particles (4) except that the amount of negative charge control agent (1) added to toner particles (4) was changed from 0.30 to 10.00 parts. The number-based median diameter D50t of the obtained toner particles (5) is 8.7 μm, and the average circularity is 0.9.
65.

[External additive (1)]
A commercially available zeolite (385HUA Tosoh Corporation) is used as the external additive (1). Table 1 shows the physical property values of the external additive (1).
[External additive (2)]
A commercially available zeolite (630HOA manufactured by Tosoh Corporation) is used as the external additive (2). The physical properties of the external additive (2) are shown in Table 1.
[External additive (3)]
A commercially available zeolite (930NHA manufactured by Tosoh Corporation) is used as the external additive (3). The physical properties of the external additive (3) are shown in Table 1.
[External additive (4)]
A commercially available zeolite (390HUA Tosoh Corporation) is used as the external additive (4). The physical properties of the external additive (4) are shown in Table 1.
[External additive (5)]
A commercially available zeolite (341NHA manufactured by Tosoh Corporation) is used as the external additive (5). The physical properties of the external additive (5) are shown in Table 1.
[External additive (6)]
A commercially available zeolite (ZEOSTAR PGS450, manufactured by Nippon Chemical Industry Co., Ltd.) is used as the external additive (6). The physical properties of the external additive (6) are shown in Table 1.
[External additive (7)]
A commercially available zeolite (330HUA Tosoh Corporation) is used as the external additive (7). Table 1 shows the physical property values of the external additive (7).
[External additive (8)]
A commercially available zeolite (Zeoram A-3 100 # manufactured by Tosoh Corporation) is used as the external additive (8). Table 1 shows the physical property values of the external additive (8).
[External additive (9)]
A commercially available zeolite (Lunamos SP-PA manufactured by Kao Corporation) is used as the external additive (9). The physical properties of the external additive (9) are shown in Table 1.
[External additive (10)]
A commercially available zeolite (Silton B, manufactured by Mizusawa Chemical Co., Ltd.) is used as the external additive (10). The physical properties of the external additive (10) are shown in Table 1.
[External additive (11)]
The silica-alumina composite oxide formed by the soot reaction is used as the external additive (11). The physical property values of the external additive (11) are shown in Table 1.

[Production Example of Toner (1)]
With respect to 100.0 parts by mass of the toner particles (1), 0.3 parts by mass of the external additive (1) and 1.7 parts by mass of hydrophobic silica fine powder surface-treated with hexamethyldisilazane (number average primary (Particle size: 7 nm) is mixed for 300 seconds using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) at a rotational speed of 4000 rpm.
Thus, the toner (1) of the present invention was obtained.

[Production Example of Toner (2) to Toner (15)]
Toners (2) to (15) were obtained in the same manner as toner (1), except that the toner particles and external additives shown in Table 2 were used to prepare toners under the conditions shown in Table 2. .

<Example 1>
When the toner (1) was used and the image evaluation described below was performed using the following image forming apparatus, there were problems caused by charging failure during printing in an extremely high temperature and high humidity environment, and excessive charging in an extremely low temperature and low humidity environment. It was excellent in suppressing harmful effects.
Hereinafter, specific evaluation means will be described.
As the image forming apparatus, a remodeling machine (process speed: 150 mm / sec) of a commercially available laser printer LBP-3700 (manufactured by HP) was used.
In the evaluation, 150 g of the toner (1) was filled in the cartridge and mounted in the cyan station, and dummy cartridges were mounted in the other stations.
Image evaluation to be described later was performed using the image forming apparatus.
The evaluation image was adjusted to a toner applied amount of 0.40 mg / cm ² , and an image having a width of 20 cm adjusted to a printing ratio of 1% at a position 5 cm from the tip was used.
Further, LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used as evaluation paper.
As an evaluation environment, the evaluation is performed in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a low temperature and low humidity environment (L / L: temperature 15.0 ° C., humidity 10.0%). RH) and a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80.0% RH).
In the evaluation of transfer failure, an environment (hereinafter referred to as cold) in which a 0 ° C. environment (temperature 0.0 ° C., humidity 50% RH) and an extremely low temperature and low humidity environment (temperature 10.0 ° C., humidity 15% RH) are alternately repeated. (Earth mode).
This cold region mode simulates a use environment where the storage temperature of the printer at night is as low as about 0 ° C. The mode will be described in detail below.
First, as a pre-treatment, a storage mode is set for 10 hours in a 0 ° C environment (temperature 0.0 ° C, humidity 50% RH), and the evaluation environment is set to a very low temperature and low humidity environment (temperature 10.0 ° C, humidity) over an hour. 15% RH), and the evaluation described later was performed.

<Fog>
After printing 0 sheets and 10,000 sheets under each environment, an entire white image was output at a process speed of 50 mm / sec on a LETTER size HP Photo Paper (HP, 220 g / m ² ).
The fog density (%) is calculated from the difference between the whiteness of the white background of the printout image and the whiteness of the transfer paper measured with a “reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). Evaluation was based on criteria.
Rank A: Good Reflection density less than 1.0% Rank B: No practical problem Reflection density of 1.0% or more, less than 3.0% Rank C: Problem Reflection density of 3.0% or more

<Fog when left unattended>
In each environment, after printing 10,000 sheets, the cartridge was placed in a machine turned off in each environment and left for 2 days.
Thereafter, an entire white image was output at a process speed of 50 mm / sec on a HP Photo Paper (manufactured by HP, 220 g / m ² ) of LETTER size.
The fog density (%) is calculated from the difference between the whiteness of the white background of the printout image and the whiteness of the transfer paper measured with a “reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). Evaluation was based on criteria.
Rank A: Good Reflection density less than 1.0% Rank B: No practical problem Reflection density of 1.0% or more, less than 3.0% Rank C: Problem Reflection density of 3.0% or more

<Transfer defect measurement method>
In the cold region mode, after making a very low temperature and low humidity environment (temperature 10.0 ° C., humidity 15% RH), an entire black image was output on LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ).
The transfer residual toner on the photoconductor during black image formation is removed by taping with Mylar tape, and the Macbeth density of only Mylar tape stuck on the paper is subtracted from the Macbeth density of the Mylar tape stuck on the paper. The evaluation was based on the following criteria based on numerical values.

Rank A: Good Less than 0.10 Rank B: No problem in practical use 0.10 or more, less than 0.20 Rank C: Problem 0.20 or more

The obtained evaluation results are shown in Table 3.

<Examples 2 to 8>
Image evaluation was performed in the same manner as in Example 1 except that the toners (2) to (8) shown in Table 2 were used instead of the toner (1) of Example 1, and the evaluation results are shown in Table 3.

<Comparative Examples 1 to 7>
Image evaluation was performed in the same manner as in Example 1 except that the toners (9) to (15) shown in Table 2 were used instead of the toner (1) of Example 1, and the evaluation results are shown in Table 3.

Claims (4)

In the toner in which zeolite is externally added to the toner particles, the zeolite contains at least silicon atoms and aluminum atoms,
A toner, wherein a ratio (%) of aluminum atoms to a total of silicon atoms and aluminum atoms contained in the zeolite is 0.3 to 22.5 .

The toner according to claim 1, wherein the zeolite has a BET specific surface area of 350 m ² / g or more and 750 m ² / g or less. The toner according to claim 1, wherein the toner particles contain a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. The toner particles are prepared by adding a polymerizable monomer composition containing at least a polymerizable monomer and a colorant to an aqueous medium, granulating the polymerizable monomer composition in the aqueous medium, and 4. It is obtained by forming polymerizable monomer composition particles and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. 5. The toner according to item.